Catalysts for the ring opening polymerization of cyclic olefins

ABSTRACT

THE MOLECULAR WEIGHT OF POLYALKENAMERS PRODUCED BY A RING-OPENING POLYMERIZATION OF CYCLIC OLEFINS IS REGULATED AND TERMINAL CARBALKOXY GROUPS FORMED THEREON EMPLOYING A CATALYST SYSTEM CONSISTING ESSENTIALLY OF (1) A TUNGSTEN OR MOLYBDENUM COMPOUND, (2) AN ORGANOALUMINUM COMPOUND, (3) AN UNSATURATED CARBOXYLIC ACID ESTER WHEREIN THE ESTER GROUP IS SEPARATED FROM THE DOUBLE BONDED CARBON ATOM BY AT LEAST ONE METHYLENE GROUP OR THE SINGLE BONDED OXYGEN ATOM OF THE ESTER GROUP AND AT LEAST ONE OF THE CARBON ATOMS BEARING THE DOUBLE BOND BEARS AT LEAST ONE HYDROGEN ATOM, AND, OPTIONALLY, (4) A COMPOUND CONTAINING ONE OR MORE HYDROXY OR SULFHYDRYL GROUPS.

United States Patent US. Cl. 252-429 B 28 Claims ABSTRACT OF THEDISCLOSURE The molecular weight of polyalkenamers produced by aring-opening polymerization of cyclic olefins is regulated and terminalcarbalkoxy groups formed thereon employing a catalyst system consistingessentially of (1) a tungsten or molybdenum compound, (2) anorganoaluminum compound, (3) an unsaturated carboxylic acid esterwherein the ester group is separated from the double bonded carbon atomby at least one methylene group or the single bonded oxygen atom of theester group and at least one of the carbon atoms bearing the double bondbears at least one hydrogen atom, and, optionally, (4) a compoundcontaining one or more hydroxy or sulfhydryl groups.

BACKGROUND OF THE INVENTION This invention relates to a process for thepreparation of polyalkenamers by the ring-opening polymerization ofcyclic olefins employing a catalyst containing a metal of Subgroups 5through 7 of the Periodic Table or a compound thereof and to novelpolyalkenamers thusproduced.

It is known that cyclic olefins containing at least one unsubstitutedring double bond can be polymerized under ring-opening conditions. Thecatalysts employed for thisring-opening polymerization are supportedcatalysts which contain a metal of Subgroups 5 through 7 of the PeriodicTable, or the compounds thereof. See German published application DAS1,072,811. Preferred catalysts are the reaction products of compounds ofthe above-mentioned metals with organometallic compounds or hydrides ofmetals of Main Groups 1 through 3 or Subgroup 2 of the Periodic Table,as well as optionally compounds which contain one or more hydroxy and/or sulfhydryl groups. See French Pats. 1394380 and 1467720; thepublished disclosures of Dutch patent applications 6510331; 6605105;6614413; 6704424; 6806208; and 6806211. The catalysts described thereincontain compounds of molybdenum or tungsten and, as organometalliccompounds, usually organoaluminum compounds. According to the publishedtexts of Dutch patent applications 6714559 and 6806209, vanadium,niobium, tantalum, rhenium, technetium, or manganese can also becomponents of such catalyst systerns.

In accordance with German unexamined published application DOS1,909,226, it is also possible to employ catalyst systems containing ahalide or an oxyhalide of molybdenum or tungsten wherein the stage ofoxidation of the metal is 4, 5 or 6, an aluminum trihalide.

With the aid of these catalysts, a great variety of polymers can beprepared with structures which are strictly regular along the polymerchains, the structure of the polymer units being exclusively dependenton the cycloolefin employed as the monomer. Thus, it is possible, forexample, to produce linear polymers by the polymerization of monocyclicolefins; polymers having recurring polymer units containing a singlering by the polymeriza- 3,798,175 Patented Mar. 19, 1974 tion ofbicyclic olefins; and, in general, polymers having recurring polymerunits which contain one ring less than the starting monomer by thepolymerization of polycyclic olefins.

The polyalkenamers produced by the polymerization of monocyclic olefinsare of particular interest for the additional reason that, depending onthe cycloolefin employed, it is possible to prepare polymers havingdiffering double bond content. Thus, polybutenamers which are free ofvinyl groups, i.e., pure 1,4-polybutadienes, are obtained fromcyclobutene, 1,5-cyc1ooctadiene, and 1,5,9- cyclododecatriene.Polypentenamers are obtained from cyclopentene which have three CHgroups disposed between the double bonds. Polyoctenamers are producedfrom cyclooctene which correspond to a completely regularsemi-hydrogenated 1,4-polybutadiene. Polydecenamers are prepared fromcyclododecene corresponding to a twothirds hydrogenated1,4-polybutadiene in which remaining double bonds are arranged in themolecule at regular intervals. Accordingly, it is possible to producepolymers, the structures of which represent variations from pure 1,4-polybutadienes, free of vinyl groups, to strictly linear polyethylenesor polymethylenes.

It is likewise known that the average molecular Weight or the degree ofpolymerization of a polymer afiects properties of the polymer and thusits usefulness in any particular field of application, as well as itscharacteristics during the production and processing. Thus, polymersolutions of equal weight concentration of polymer are more viscous, thehigher the molecular weight of the polymer in solution. Thus,difficulties are encountered with solutions of very high-molecularpolymers, e.g., during the polymerization, for example, in the mixing orobtaining satisfactory heat exchange, and increased energy requirementsfor the agitating step result. Also, the further processing of veryhigh-molecular polymers is difficult. For this reason, they are oftendegradated mechanically, chemically, or thermally prior to the finalshaping procedure, e.g., injection-molding, extrusion, or calendering.

The polyalkenamers obtained during the ringopening polymerization ofcycloolefins are normally very highmolecular. Because of theabovedescribed difiiculties with polymers of very high molecular weight,attempts have been made in the prior art to develop processes forregulating the molecular weight of the polymers producible by a greatvariety of polymerization methods. In the polymerization of a-olefinswith organometallic mixed catalysts, the so-called hydrogen regulation,i.e., polymerization in the presence of a certain partial hydrogenpressure, proved useful. Other possibilities for controlling themolecular weight of a-olefin polymers were varying the catalystcomponents, elevating the temperature or adding alkylzinc oralkylcadmium compounds during the polymerization.

Although organometallic mixed catalysts or related catalyst systems arealso employed in the ring-opening polymerization of cycloolefins, themethods for molecular weight regulation employed in the polymerizationof the a-olefins either are unsuccessful or exhibit definitedisadvantages which make the use of such methods ditficult, if notimpossible. Thus, hydrogen, for example, up to an excess pressure of 4atmospheres exerts practically no influence at all on the molecularweight of the polyalkenamers prepared by the ring-opening polymerizationof cycloolefins. Even if hydrogen were eiiective at pressures higherthan those mentioned above, the hydrogen regulating method would requireincreased investment costs, since the plant would have to be designedfor pressures which do not occur in the unregulated ring-openingpolymerization of the cycloolefins which, under normal pressure, arepresent in the liquid phase or in solution at the polymerization icetemperature. Although the molecular weight of the polyalkenamers can bereduced 'by employing a higher polymerization temperature, the yield andthe steric uniformity of the polymers are impaired in so doing.Moreover, due to the temperature sensitivity of the mixed catalystscustomarily employed for the ring-opening polymerization ofcycloolefins, such catalysts become inactive above 40-50 C. in a shortperiod. Also, modifications of an optimal catalyst system can stronglyimpair yield. See, for example, Dutch patent application 6605105, p. 16.

The last of the above-mentioned methods for controlling the molecularWeight during the polymerization of a-olefins with organometallic mixedcatalysts, i.e., using an alkylzinc or alkylcadmium compound as thecontrolling agent, is of little practical use, even if it were effectivein the ring-opening polymerization of cycloolefins, because such zincand cadmium compounds are very toxic and can be prepared only withdifliculty and thus are expensive.

The only process heretofore known wherein polymers are obtained whichexhibit improved processability is de scribed in British Pat. 1,098,340.In this process, cyclic monoolefins are copolymerized under ring-openingin the presence of a conjugated diolefin, such as, for example,butadiene, isoprene, or 1,3-pentadiene. The thus-produced copolymerscontain polymer units derived from both the cycloolefin and theconjugated diolefin, in varying molar ratios.

As shown in Comparative Experiments N through T in Table 3, conjugateddienes, although they influence the molecular weight of thepolyalkenamers produced in polymerizations conducted in their presence,also are more or less strong catalyst poisons. Thus, for example, thepresence of only 1 mol percent of 1,3-butadiene, 5 mol percent ofisoprene, 5 mol percent of 2,3-dimethyl-1,3- butadiene, or mol percentof 2,4-hexadiene, results in the complete inhibition of thepolymerization catalyst and no polymer is obtained. Cyclic conjugateddiolefins also cause a pronounced lowering of the yield of polymer.Moreover, it is not possible using such dienes as polymerizationregulators to produce polymers which are waxy or oil-like productshaving very low molecular weights, e.g., about 500-5000.

In our prior filed application Ser. No. 70,497 filed Sept. 8, 1970, weclaim a process for the regulation of molecular weight of polyalkenamersby the addition of monoolefins, preferably u-olefins, during thepolymerization. The molecular weight of polyalkenamers can be regulatedwith a very high degree of success by this process. However, there is agreat interest in polymers having functional terminal groups, which canbe employed for further reactions, such as, for example, crosslinkingreactions or for the construction of other defined polymer structures,e.g., block copolymers or stellate polymers. For example, a stellatestructure is obtained by the reaction of a unilaterallylithium-terminated polymer, e.g., a polybutadiene or polystyreneproduced in a polymerization which employs butyllithium as the catalyst,with a trior tetrahalogen compound, such as, for example,methyltrichlorosilane, silicon tetrachloride, or carbon tetrabromide. Achain of a polymer terminating at both ends in halogen can be reactedwith a unilaterally metal-terminated chain of another polymer to formblock copolymers. Polymer chains terminating in hydroxyl groups can becross-linked with di-, tri-, or polyisocyanates or other polyfunctionalcompounds, such as, for example, acid chlorides of polybasic acids.These examples are typical but not complete and merely illustrate thatsuch reactions of telechelic polymers (US. Pat. 3,244,664) have gainedincreasing importance in recent times. Functional end groups alsoinfluence the practical application properties of the polymers andeffect, for example, an improved adhesion to surfaces and/or an improvedcompatibility with other polymers. Thus, there is an increasing need forprocesses yielding polymers having defined functional end groups.

Accordingly, it is an object of the present invention to provide aprocess which makes possible, in a simple manner, to simultaneouslyregulate the molecular weight of polyalkenamers produced by thering-opening polymerization of cyclic olefins and to introducefunctional terminal groups into the polymer molecule. Another object isto provide novel polymers thus-produced. Other objects will be apparentto those skilled in the art to which this invention pertains.

SUMMARY OF THE INVENTION According to this invention, the molecularWeight of polyalkenamers produced by the ring-opening polymerization ofcyclic olefins employing a catalyst containing a metal of Subgroups 5 to7 of the Periodic Table and conducting the polymerization in thepresence of an unsaturated carboxylic acid ester wherein the ester groupis separated from the double bonded carbon atom by at least onemethylene group or the single bonded oxygen atom of the ester group andat least one of the carbon atoms bearing the double bond bears at leastone hydrogen atom.

DETAILED DISCUSSION The cyclic olefin and cycloolefin employed in theprocess of this invention are unsaturated hydrocarbons contain ing oneor more rings, at least one of which contains at least one unsubstitutednon-conjugated double bond.

The cycloolefins polymerized according to the process of this inventionpreferably contain 4 to 12 ring carbon atoms and a total of 4 to 20,preferably 4 to 15 carbon atoms; from 1 to 3, preferably 1 to 2 rings,which can be fused or separate cycloaliphatic rings; whose ring carbonatoms are unsubstituted or one or more of which are substituted withlower-alkyl, e.g., of 1 to 4 carbon atoms, cycloalkyl, e.g., of 5 to 7carbon atoms, or aryl, alkaryl or aralkyl, e.g., of 6 to 10 carbonatoms.

Preferred classes of starting cycloolefins are the following:

(a) Those containing 1 to 2 non-conjugated double bonds, preferably one;

(b) Those containing 1 to 2 rings, preferably one;

(c) Those of (a) and (b) containing two fused rings;

(d) Those of (a), (b), and (0) containing 0-2 loweralkyl groups as thesole substituents on the ring carbon atoms, preferably 0;

(e) Those of (d) containing 1-2 methyl groups as the sole substituentson the ring carbon atoms;

(f) Those of (a), (b), (c), (d), and (e) wherein the unsiaturated carbonatoms each bear a hydrogen atom; an

(g) Those of (a), (b), (c), (d), (e) and (f) wherein the ring of thecycloolefin containing the unsaturation contains 5 or 7 to 12 ringcarbon atoms.

Examples of cycloolefins which can be polymerized according to theprocess of this invention are cyclobutene, cyclopentene, cycloheptene,cyclooctene, cyclononene, cyclodecene, cycloundecene, cyclododecene,cis, cis-1,5 cyclooctadiene, l-methyl-l,5-cyclooctadiene, 3,7-dimethyl-1,5-cyclooctadiene, 1,5,9-cyclododecatriene, 4,5-dimethyl- 1,4,7cyclodecatriene, cis,trans-1,5-cyclodecadiene, norbornene,dicyclopentadiene, dihydrodicyclopentadiene, and 4-phenylcyclooctene,and mixtures thereof. Cycloolefins which cannot be polymerized withring-opening, e.g., cyclohexene and the derivatives thereof, are notemployed as starting monomers in the polymerization process of thisinvention.

The polymerization of this invention is conducted in the presence, as apolymerization regulator, of an unsaturated carboxylic acid estercontaining at least one acyclic carbon-carbon double bond, i.e., whereinthe double bond is not part of a ring, which is separated from thecarbonyl group of the ester grouping by at least one single bondedcarbon atom, e.g., a methylene group, and/ or by the oxy oxygen atom ofthe ester group and wherein at least one .5 of the double bonded carbonatoms bears a hydrogen atom as a substituent.

Of the esters in which the unsaturation is in the alcohol portion of themolecule, preferred are vinyl and allyl esters, especially of straightor branched chained alkanoic or cycloalkanoic saturated monoanddicarboxylic acids containing 1-20 carbon atoms and substituted by -3,preferably 0 or 1, halogen atoms, preferably chlorine or bromine, and ofaryl monoand dicarboxylic acids containing 7-12 carbon atoms andsubstituted by 0-5, preferably 0, 1 or 2, halogen atoms, preferablychlorine or bromine.

Examples of such unsaturated esters are compounds of the formula whereinR and R each are hydrogen, alkyl, cycloalkyl, aryl, alkaryl in thecorrespondinb halogenaed groups, and a and d each are 0 or 1, with theproviso that at least one a and d is 1, and b and 0 each are 0 or anypositive integer.

When R or R are other than hydrogen, R and R can be straight-chain orbranched saturated alkyl of l-20, preferably l-12, carbon atoms, orcycloalkyl containing 3-12, preferably -12 ring carbon atoms, 1, 2 or 3separate or fused rings, and 3-20, preferably 5-12 carbon atoms,unsubstituted or substituted by one or more halogen atoms. Examples ofaryl are those containing 6-14 carbon atoms and 1, 2 or more separate orfused rings, unsubstituted, or substituted by unsubstiuted orhalogenated alkyl or cycloalkyl as defined above.

Examples of alkyl are methyl, ethyl, propyl, isopropyl, butyl, isobutyl,tert.-butyl, hexyl, heptyl, octyl and higher straight and branched chainalkyl. Cycloalkyl includes cyclopropyl, cyclobutyl, cyclopentyl,cyclohexyl, 2-methyl cyclopentyl, 2,6 dimethylcyclopentyl, 4methylcyclohexyl, 3,5 dimethylcyclohexyl, 2 methylcyclohexyl,cycloheptyl, cyclooctyl, decahydronaphthyl, and the corresponding groupssubstituted on one or more ring carbon atoms by alkyl of 1-4 carbonatoms. Aryl includes phenyl, p-diphenyl, naphthyl, ar-lower-alkyl, e.g.,p-benzylphenyl, benzyl, phenethyl, 2-phenyl propyl and benzhydryl,tetrahydronaphthyl, 6 tetrahydronaphthyl indenyl, dihydroindenyl.Alkaryl includes aryl substiuted on one or more ring carbon atoms byalkyl of 1-4 carbon atoms, preferably methyl, e.g., p-tolyl, sym.-xylyl,etc.

When the double bond of the unsaturated ester is positioned on thealcohol side of the ester group, i.e., in the above formula, a=1, b canbe 0, or a positive integer, e.g., 1, 2, 3-6 or higher. When the doublebond is positioned on the acid side of the ester group, i.e., in theabove formula, if d=1, then c must be at least 1, i.e., 1, 2, 3-6 orhigher.

Examples of preferred unsaturated esters wherein the alcohol portionthereof is unsaturated are vinyl and allyl esters, wherein the vinyl orallyl group is unsubstituted or substituted by one or more straight orbranched chain alkyl groups, e.g., containing l-12 carbon atoms, e.g.,methyl, ethyl, propyl, butyl, hexyl, octyl and decyl, or aryl as definedabove, e.g., phenyl, or alkanoic and alkanedioic acids containing, e.g.,1-8 carbon atoms, e.g., acetic, propionic, butyric, octanoic, succinic,malonic, fumaric, adipic, and of aryl and aralkyl carboxylic anddicarboxylic acids, e.g., benzoic, phenylacetic and phthalic acids andthe corresponding halogenated, preferably chlorinated acids, e.g.,chloroacetic and dichloroacetic acid.

Examples of preferred unsaturated esters wherein the acid portionthereof is unsaturated are allyl, e.g., of 1-8 carbon atoms, e.g.,methyl, ethyl, propyl, octyl, esters of alkenoic acids containing 1-21carbon atoms, e.g., 3-butenic, 3-pentenic, 4-pentenic, 3-, 4- andS-hexenic, oleic, brassidic and behenic acids and other straight andbranchchained unsaturated acids and the corresponding halogenated,preferably chlorinated or brominated, alkyl esters thereof, e.g.,fi-chloroethyl esters.

Especially preferred are vinyl and allyl esters of unsubstituted andoptionally halogenated monoor dicarboxylic acids. Representativeexamples of this preferred class are vinyl propionate. vinylisobutyrate, vinyl stearate, divinyl adipate, methylvinyl adipate, vinylpivalate, vinyl chloroacetate, allyl propionate, allyl butyrate, allylchloroacetate, allyl dichloroacetate, and diallyl phthalate. Especiallypreferred are vinyl acetate and allyl acetate.

Other examples of unsaturated esters are crotyl acetate, cinnamylpropionate, isopropenyl benzoate, 2-phenylbuten (l) yl-4-acetate,1,4-diacetoxybutene-2, oleyl acetate, 3 hexene-l,6-diol distearate,ll-acetoxy-undecene-l, octen (1) yl 3 butyrate, p-allyl-benzyl formate,3 vinylcyclooctyl acrylate, methyl oleate, ethyl undecylenate, thedimethyl ester of dihydromuconic acid (dimethyl ester of 3-hexenedioicacid), or the ,B-chloroethyl ester of vinylacetic acid.

If unsaturated esters employed as the regulators are esters of monobasicmonounsaturated esters, e.g., those having a carbalkoxy group on oneside only of the double bond, e.g., allyl acetate, the polymers producedby the process of this invention possess, on the average, onecarboxyalkyl group per macromolecule. However, macromolecules can alsobe produced which have either no carbalkoxy end group or two carbalkoxyend groups.

.Macromolecules having two carbalkoxy end groups are always obtainedwhen using as regulators esters having carbalkoxy groups on both sidesof the double bond, for example, 1,4-diacetoxybutene-2, the dimethylester of dihydromuconic acid and the methyl ester of p-acetoxy-p'-stilbene-carboxylic acid.

A surprising peculiarity of the esters of unsaturated alchols with b=0or 1, i.e, vinyl or allyl/esters which may be substituted by R asdefined before is that they exert, even in very small quantities rangingin the order of magnitude of catalyst concentration, a favorableinfluence on the velocity and yield of the polymerization, in additionto controlling molecular weight. This activator effect cannot beexplained by means of any of the heretofore known theories regarding themechanism of the ringopening polymerization of cyclic olefins.

With the aid of these activators, it is also possible to developcatalyst systems based on tungsten hexachloride and ethylaluminumsesquichloride or diethylaluminum chloride, which normally exhibit onlyminor catalytic activity, which are highly satisfactory polymerizationcatalysts. Ethylaluminum dichloride containing catalysts, which haveheretofore shown the highest activity, is manufactured in smallerquantities than the two other abovementioned ethylaluminum halogenidesand, moreover, can be handled only in dilute solutions, due to itsmelting point of +32 C. Furthermore, catalysts containing ethylaluminumdichloride have a strong tendency to promote secondary reactions of acationic type. Thus, for example, they have an alkylating effect onaromatics and polymerize branched olefins, which can result in gelling.

By employing the activating regllators or regulating activators of thisinvention, a considerable increase in catalyst activity is alwaysattained, even in the case of catalysts containing ethylaluminumdichloride, so that high conversion rates can be obtained, even when thepolymerization is conducted in dilute soltuions, which reactionordinarily progresses very unsatisfactorily, especially in case ofcyclopentene. This is also advantageous from the view point of processtechnique, for it is possible to polymerize a higher proportion of themonomer rather than being forced, as, as in case of bulk polymerization,to utilize the monomer as the solvent and work with small conversions,due to the viscosity of the thus-produced polymer solution, and toregenerate and recycle the larger portion of the monomer. Besides,especially in the case of cyclopentene, the polymerization need nolonger be conducted at the very uneconomical low temperatures of20 to 30C. Instead, the same or even still higher yields are obtained underconditions which are technically and economically more advantageous to20 C.).

The ring-opening polymerization of cyclic olefins can be conducted byconventional procedures employing known catalysts. Thus, suitablecatalysts are supported catalysts containing the metal of Subgroupsthrough 7 of the Periodic Table, for example, in the form of thecarbonyl, sulfide, or superficially reduced oxide on a support such as,for example, aluminum oxide, aluminum silicate, or silica gel. Alsosuitable are mixed catalysts, e.g., containing a compound of a metal ofGroups 5 through 7 of the Periodic Table and an organometallic compoundor hydride of a metal of Main Groups 1 through 3 or Subgroup 2 of thePeriodic Table and optionally, also a compound containing one or morehydroxy and/or sulfhydryl groups. Also suitable are catalysts containinga halide or oxyhalide of molybdenum or tungsten wherein the degree ofoxidation of the metal is 4, 5, or 6, and which contain an aluminumtrihalide. Preferably, mixed catalysts are employed containing amolybdenum compound or especially a tungsten compound. Preferredorganometallic compounds are organolithium, organomagnesium andorganoaluminum compounds, especially methylaluminum dichloride,ethylaluminum dichloride, methylaluminum sesquichloride, ethylaluminumsesquichloride, dimethylaluminum chloride and diethylaluminum chloride.Compounds containing one or more OH and/ or SH-groups optionally can beemployed concomitantly as a catalyst component, e.g., water, hydrogensulfide, hydrogen peroxide, alkyl hydroperoxides, mercaptans,hydrodisulfides, alcohols, polyalcohols, polymercaptans andhydroxymercaptans. Saturated and unsaturated alcohols and phenols, viz.,n-propanol, n-butanol, sec.- butanol, isobutanol, allyl alcohol, crotylalcohol, phenol, 0-, m-, and p-cresol, 00- and B-naphthol, eugenol andbenzyl alcohol, especially methanol, ethanol, isopropanol, ortert.-butanol, are preferred.

The polymerization can be conducted continuously or discontinuously. Thereaction temperature can vary widely, e.g., between 70 C. and +50 C.However, temperatures between 30 and +30 C. are preferred.

The amount of regulator which is added and, as a consequence, themolecular weight of the polymers produced, can be varied widely withoutany disadvantageous effects on the yield and the stereospeci ficity ofthe polymerization. When employing, for example, cyclobutene orcyclopentene as the monomer, it is thus possible to produce rubber-likeproducts of a high Mooney viscosity, which can be extended with a largeamount of oil, as well as other readily processable rubber types.

It is also possible to manufacture highly tacky products of lowviscosity and syrupy to oily liquids which can be utilized, for example,as drying oils directly, or after an additional reaction, as binders forvarnishes or coating agents.

The amount of regulator needed to attain a product of a specificconsistency depends, inter alia, on the type of the monomer employed,the type of regulator employed, the catalyst employed, and the selectedpolymerization reaction conditions. The exact amount of regulator canreadily be determined by a few preliminary experiments.

The amount of unsaturated ester employed can vary from about 0.001-molar percent, based on the monomer. Generally, the use of about0.0001-5, preferably about 0.003-2, more preferably about 0.01-5mol-percent, and most preferably about 0.052 mol-percent, of unsaturatedester, based on the monomer employed, results in the production ofpolyalkenamers having molecular Weights in the range of commercialelastomers or thermoplastics. The addition of between about 6 and 20molar percent, preferably between about 7 and 15 molpercent of theregulator, based on the monomer employed, generally is required for theproduction of lowviscosity to oily products.

These data apply when using regulators which do not simultaneouslyincrease the polymerization velocity and the polymer yield. In contrastthereto, when using activating regulators, regulators, about one-tenthof the above quantities often is sufficient for the preparation ofpolyalkenatmers having molecular weights in the range of commercialelastomers and thermoplastics.

It is to be noted that the unsaturated esters, as Lewis bases (electrondonors) form complexes with the other components of the catalyst andthereby can inactivate the latter. Therefore, it is necessary to employthese compounds either in the form of complexes with Lewis acids or toensure, by an appropriate dosing of the organometallic compound, thatthe catalyst is always present in an excess of the oxygen atoms whichare effective as electron donors in the regulator compound employed.Otherwise, no polymerization takes place.

Since the activating efiect of the esters of vinyl and allyl alcohols isclearly perceptible with the addition of a very small amount thereof,e.g., approximately 1 molar percent of the heavy metal component of thecatalyst, especially in case of tungsten compounds and particularly incase of tungsten hexachloride, these activating regulators can also beconsidered to be components of the catalyst system and can be employedprimarily for the purpose of improving yield. Any desired reduction ofthe molecular weight of the polymer lower than it would be obtained withthe use of these additives by themselves, can be achieved by theadditional use of other regulators, for example the previously proposeda-olefins. This combination of activating regulators and a-olefins isparticularly advantageous when very low-molecular products are to bemanufactured, e.g., oils, and no importance is attributed to functionalend groups of the polymer because such end groups would not olfer anyspecial advantage for the intended purpose for which the products are tobe used.

It is to be noted that when the conversion of monomer is increased,i.e., when the yield of polymerizate is improved, the molecular weightof the thus-obtained polymer is likewise raised. Conversely, when asubstantial increase in conversion is accompanied by only a slightincrease in molecular weight (or RSV), this must be still considered tobe due to a regulation of molecular weight by the added compound.

The polymerization process of this invention is preferably conducted insolution. For this purpose, inert solvents inert under the reactionconditions are employed, e.g., benzene, cyclohexane, methylcyclohexane,isopropylcyclohexane, Decalin, hydrogenated kerosene, parafiin oil,methylene chloride, trichloroethylene and preferably hexane, heptane,octane, and perchloroethylene. The amount of solvent employed can varywidely, e.g., 5 to 2,000% by weight, preferably 50 to 1,000% by weight,based on the monomer employed. Low-molecular oily polymers can alsoadvantageously be prepared without a solvent by mass polymerization, solong as the viscosity of the thus-reacted mixture remains reasonablylow.

The amount of catalyst which need be employed is very low. For example,in case of tungsten hexachloride, only about 0.5-2 millimols per literof reaction volume, or about 1 mol per 1,000-5,000 mols of monomer, isrequired. When using an activating regulator, this quantity can bereduced to approximately one-tenth the amount, in spite of the improvedyield. The concentration of organometallic catalyst component dependsprimarily on the purity of the monomer and the solvent employed, i.e.,the amount of moisture, peroxides, proton-active impurities, such asalcohols, acids, and other compounds reacting with alkyl metals, such asethers, amines, ketones, aldehydes, etc., present therein. When themonomer and the solvent are subjected to a very thorough preliminarypurification and the reactants are handled with strict exclusion of airin thoroughly dried reactors, molar ratio of heavy metal compound toactive alkyl metal, i.e., an

alkyl metal which has not been bound or destroyed by impurities or anyadditional additives present, of about 1:4 to 1:1, preferably less than1:1, is generally sufi'lcient. Outside of this range, the catalysts arenormally less active.

As in the case of regulating the molecular weight of polyalkenamers withmonoolefins, surprisingly it is not necessary in the process of thisinvention that the regulator be present at the beginning of thepolymerization in order to obtain the desired eifect. The regulator can,if desired, be added after polymerization has begun. All that isrequired is that the catalyst is still active, i.e., the regulator mustbe added prior to the inactivation of the catalyst. It is thus possibleto use regulators which tend to form homopolymers which are insoluble inthe reaction mixture if exposed to the catalyst, either by themselves orin a mixture with cycloolefins at the beginning of the polymerization,and thus inactivate the catalyst by inclusion in the insoluble polymer,or which enter into secondary reactions with the catalyst componentsprior to the actual formation of the catalyst, but which do not react insuch a manner with the finished catalyst. The tendency of a regulator topromote homopolymerization or enter into such secondary reactions canquickly be determined by preliminary experiments. Because of thischaracteristic, it is also possible when an unforeseen rise in theviscosity of a polymerization batch takes place, as occasionallyhappens, to keep the contents of the kettle stirrable by adding theregulator before inactivation of the catalyst, thus avoiding theextensive work connected with emptying a batch which has become tooviscous or even gelled.

The preferred catalyt systems employed in the polymerizations of thisinvention are those comprising:

( l) A tungsten or molybdenum compound;

(2) An organoaluminum compound;

(3) An ester of vinyl alcohol or of allyl alcohol; and, optionally,

(4) A compound containing one or more hydroxyl and sulfhydryl groups.

Preferred aspects of the catalyst systems of this invention comprise oneor more of any of the following:

(a) Component (1) is tungsten hexachloride or tungsten oxytetrachloride;

(b) Component (2) is an alkyl aluminum halide, preferably ethylaluminumdichloride, ethylaluminum sesquichloride or diethylaluminummonochloride;

() Component (3) is vinyl acetate or allyl acetate;

(d) Component (4) is ethanol;

(e) The molar ratio of component (1) to component (2) is less than 1:1;

(f) The molar ratio of component 1) to component (3) is less than 100:1,preferably less than :1.

(g) The molar ratio of component 1) to component (4) is about 1:0.1 to1:2; and/or (h) The molar ratio of component (2) to component (3) isgreater than 1:1.

After the termination of the polymerization reaction, the polyalkenamerscan be isolated and purified in a conventional manner. If thepolyalkenamers are obtained in solution or in the liquid phase, theresidues of the catalyst can be removed with an alcohol or othercompound having an acidic hydrogen, by washing out the polymercontainingphase with an aqueous or aqueous-alcoholic solution of agents having adissolving effect on the catalyst residues, which latter are firstpresent as an alcoholate or a salt of the other compound having anacidic hydrogen atom used to remove the catalyst. Such substances with adissolving effect on the catalyst are, for example, acids, bases, orcomplex-forming agents, such as acetylacetone, citric or tartaric acid,ethylenediaminetetraacetic acid, nitrilotriacetic acid, etc.

After the catalyst has been removed, the polymers are separated byprecipitation, e.g., by pouring into a precipitant such as, for example,methanol, isopropanol, or acetone, or distilling off the solvent, e.g.,by blowing in steam, or by introducing the polymer solution throughnozzles into hot water. When the polymer can be precipitated from thesolution of the monomer in the form of flakes or a powder, the polymercan first be separated, e.g., by filtration, centrifuging, or decantingfrom the liquid and thereafter treated to remove the catalyst residues.

In order to protect the polyalkenamers against oxidation, gelling, andother aging phenomena, it is possible to add stabilizers thereto, e.g.,aromatic amines or the sterically hindered phenols, at various stages ofprocessing. Also, an optional further purification step can be conductedby reprecipitating the polymer if this should be necessary, to obtain aproduct of the desired purity. After these operations, the polymer canthen be dried in a conventional manner.

In contrast to the previously known polyalkenamers which, althoughcalled linear polymers, in reality, are macrocyclic compounds, thepolyalkenamers prepared in accordance with the process of this inventionare truly linear polymers of a strictly regular structure with exactlydefined terminal groups. Such polymers have not heretofore beenproduced.

The polyalkenamers produced in accordance with the process of thisinvention are, in contrast to the polymers known heretofore whichalthough called linear polymers are in reality marcrocyclic compounds,true linear polymers of a strictly regular structure with exactlydefined end groups, which have not been described heretofore.

By the ring-opening homopolymerization according to the process of thisinvention of monocyclic monoolefins of the general Formula I 0H=0H C I3polymers of the general Formula II are obtained:

wherein in both instances R is hydrogen or a straightchain or branchedsaturated alkyl of 1-6 carbon atoms, saturated cycloalkyl of 3-6 carbonatoms or aryl of 6-10 carbon atoms, and X, m and y have the values givenbewherein X, y and m have the values given below.

By the ring-opening homopolymerization of monocyclic diolefins of thegeneral Formula IV CH=CH III Ra Ra R4 IV there are obtained polymers ofthe general Formula V wherein, in Formulae IV and V, X, y and have thevalue given below, and R R R and R which are alike or different have thesame value as R Thus, R and/or R groups can be disposed throughout thepolymer molecule. In other words, n of the R groups and/or 0 of the Rcan be hydrogen or 1 to n of the R groups and/or 1 to o of the R groupscan also be alkyl or aryl, respectively.

The same applies to R and/or R groups, which likewise can both behydrogen or either or both can also be identical or different alkyl oraryl groups. Thus, by the ring-opening homopolymerization ofunsubstituted monocyclic diolefins of Formula IV wherein R R R and R arehydrogen, there are obtained polymers of the general Formula VI.

Homopolymers of the general Formula VII are produced by the ring-openingpolymerization of monocyclic triolefins of the general Formula VIIICH=CH l 5 1 s 0 q R R11 Ru VIII wherein X and y have the values givenbelow and R R R R R R and R which can be alike or different, have thesame values as R The various R R and/or R groups can be identical ordifferent groups, i.e., all p of the R groups, all q of the R groupsand/or all r of the R groups can be hydrogen; or from 1 to p of the Rgroups, 1 to q of the R groups and/or 1 to r of the R groups can,respectively, be an alkyl or aryl group. The same is true of the R R Rand/or R which likewise can all represent hydrogen, or individually orseverally, can be identical or different alkyl or aryl groups.

By the ring-opening homopolymerization of norbornene there are obtainedpolymers of the general wherein X and y have the values given below.

Polymers containing two or more of the abovedescribed polymer units in astatistical distribution or in larger block sequences are producedduring the ringopening copolymerization of two or more of theabovedescribed cycloolefins in the presence of the claimedpolymerization regulators.

In Formulae II, III, V, VI, VII and IX, m is the integer 2 or 3 or aninteger from 5 to 10 inclusive; n and 0 each integers from 1 to 7, thesum of which is an integer from 3 to 8; p, q, and r each are the integer1 or 2; any y is an integer from 2 to about 50,000, preferably 5 toabout 20,000.

The novel polyalkenamers of this invention are characterizedstructurally by their novel terminal groups. These groups are alkylideneradicals derived from the unsaturated ester employed in thepolymerization as the polymerization regulator. Thus, in Formulae II,III, V, VI, VII and IX, X is an alkylidene residue corresponding to oneof the segments of the unsaturated ester employed during thepolymerization wherein the division of the unsaturated ester is effectedat the double bond, e.g. an unsaturated ester of the formula OH=CH-OCOCH may be divided in the segments CH and=CH-OCOCH Both segmentsrepresent an alkylidene residue.

The solid polymers or oligomers of the general F01- mula II, III, V.VII, and IX exhibit RSV-values (reduced specific viscosity values) of001-1000 dl./g. The lowmolecular weight fluid polymers have averagemolecular weights in the range of about 500 to 25,000. Average molecularweights mean the arithmetic means of the molecular weights.

In former publications Natta and DallAsta stated (Angew. Chem. 76, 765(1964) and J. Pol. Sci. 6, 2405 (1968) that polyalkenamers prepared byring-opening polymerization of cycloolefins have a strictly linearstructure. Later on Calderon alleged that those polyalkenamers are inreality macrocyclic compounds (I. Am. Chem. Soc. 90, 4133 (1968)). Thisproposition was proved by isolation and identification of macrocyclicoligomers with polymerization rates up to 11 (Adv. Chem. Ser. 91, 399(1969) The novel polyalkenamers can unexpectedly and readily be workedup, as they have a lower reduced melt viscosity. Therefore they may beworked up by lower temperature, e.g., by calendering, rolling orinjection moulding, whereby the energy-costs are much smaller.

Without further elaboration, it is believed that one skilled in the artcan, using the preceding description, utilize the present invention toits fullest extent. The following preferred specific embodiments are,therefore, to be construed as merely illustrative, and not limitative ofthe remainder of the disclosure in any way whatsoever. Unless statedotherwise, the reduced specific viscosity (RSV) and the gel contentswere determined in benzene at 25 C.

EXAMPLES 1-l6 AND COMPARATIVE EXPERIMENTS A-E Into a three-utbe l-literglass flask with agitating unit and reflux condenser with a droppingfunnel attached thereto were introduced, respectively, ml. (77.8 g.) ofcyclopentene and ml. of hexane and were brought under an atmosphere ofextremely pure nitrogen, to the reaction temperature by cooling orheating, and are mixed with the components of the polymerizationcatalyst. After the predetermined reaction period, the catalyst wasdestroyed by the addition of 50 ml. of methanol containing 3 g. ofpotassium hydroxide and 2 g. of 2,6-di-tert.- butyl-p-cresol (Ionol).After the addition of 100 ml. of distilled water and 50 ml. of methanol,so that a second phase containing 50% methanol was formed, the reactionmixture was then further agitated for three hours, to Wash out thecatalyst residues. The aqueous-methanolic phase was then removed bypipetting and the reaction mixture was washed twice with 50% aqueousmethanol. The polymer was then precipitated by pouring the organic phaseinto 3 liters of methanol. The precipitated product was dissolved onceagain in 250 ml. of hexane, for purposes of an additional purification,and reprecipitated with methanol to which was again added 2 g. ofstabilizer (Ionol). After decoating the polymer for 2 hours with 500 ml.of pure methanol, it was dried for 40 hours at 50 C. in a vacuum dryingchamber. The thus-purified polymer was employed for determining theyield and the analytical data. In each case, such a blank test(designated in the table by capital letters) was conducted to excludesources of errors due to changing impurities in the solvent, themonomer, or the catalyst components, in parallel to the polymerizationsemploying one of three regulator olefins (numbered examples). Theregulators to be tested were admixed with the monomers in the examples.In Table 1,

the amount of regulator is set forth in molar percent, based on themonomer employed.

TABLE 1 Polymerization of cyclopentene (100 ml.=77.8 g. per experiment)in hexane (150 ml. per experiment). Catalyst system: 0.5 millimol oftungsten hexachlorlde/0.5 millimol of ethanol/changing amounts ofethylaluminmn dichloride. Polymerization temperature: C. Polymerizationtime: 2.5 hours.

Regulator Polymer 1511141012 in Amount Transthe catalyst (mol Yield RSVcontent Gel Experlmentnumber (mmol) percent) Name (g.) (dL/g.) (percent)(percent) 3 6.9 4.6 86 7 4 0.1 Vinylacetate..... 12.8 1.8 90 2 4 0.1Allyl acetate 16.2 2.0 81 4 4 0.1 Crotyl 6.8 3.2 91 2 3 8.1 3.0 80 214.4 1.0 viii/[371 pmpinnate 40.9 1.8 74 3 25.8 1.0 ethylvinyl adipate31.7 2.9 66 3 25.8 1.0 Diallyl sucvinate 19.8 2.5 82 22 3 11.1 3.0 81 614.4 1 0 Vinyl stearate 40.0 1.0 81 8 14.4 1 0 0ctadecen-(9)-yl acetate19.7 1.7 74 4 14.4 1 0 Methyl oleate 18.2 2.0 84 7 4 15.2 3.74 89 2 14.41.0 Allyl chloroacetate 34.6 0.82 94 7 14.4 1.0 Allyldichloroacetate22.4 0.77 ca. 100 14 25.8 1.0 Diallyl phthalate 21.7 1.55 73 2 4 16.34.39 94 3 15.4 1.0 Buten-(D-yI-3-acetate 27.4 1.28 91 2 25.8 1.0 Divinyladipate 48.5 1.03 81 4 15.4 1.0 Vlnylisobutyrate 47.0 0.91 76 3 15.4 1.02-pheny1buten-(1)-yl-4-acetate 21.8 2.56 87 2 EXAMPLE 17 AND COMPARATIVEEXPERIMENT F Copolymerization of cyclopentene and cyclooctene 50 ml.(38.9 g.) of cyclopentene and 50 ml. (42 g.) of cyclooctene weredissolved in 150 ml. of hexene and cooled to 0 C. Then, 0.5 millimol oftungsten hexachloride, 0.5 millimol of ethanol, and millimols ofethylaluminum dichloride and 2 millimols of vinyl acetate were addedthereto under agitation. After 2.5 hours, the catalyst was decomposedand the polymer was worked up in the manner described in Examples 1-16.There was thus obtained 52.9 g. of a polymer having a reduced specificviscosity (RSV) of 2.1 dl./ g. The polymer contained 32 molar percent ofpolyentenamer units (determined by nuclear resonance analysis) theremainder being polyoctenamer units. 78% percent of the double bondsthereof detachable by ultrared analysis were present in thetrans-configuration, the remainder (22%) were present in thecis-configuration.

In a comparative experiment wherein the vinyl acetate and the amount ofethylaluminum dichloride required for compensating the donor effect ofits ester group (2 millimols) were omitted, there was obtained only 3.4g. of a polymer having a reduced specific viscosity of 1.5 dl./g., acontent of polypentenamer units of 57 molar percent and a proportion oftrans-double bonds of 84%.

It can be seen from the above that the polymerization of cyclopentene at0 C. is strongly inhibited by the presence of cyclooctene but theaddition of an activating regulator, in this case vinyl acetate,overcomes this inhibition and makes possible the production ofcopolymers in high yield.

Similar results are obtained by employing cyclododecene in place ofcyclooctene and/or allyl acetate in place of vinyl acetate.

EXAMPLE 18 AND COMPARATIVE EXPERIMENTS G, H, AND I Use of ethylaluminumsesquichloride 100 ml. (77.8 g.) of cyclopen-tene was diluted with 150ml. of hexane and cooled to 0 C. Thereafter, 0.5 millimol of tungstenhexachloride, 0.5 millimol of ethanol, 4 millimols of ethylaluminumsesquichloride and 1 millimol of vinyl acetate were added underagitation. After'a reaction amples 1-16- There was thus obtained 23.5 g.of a polypentenamer having a reduced specific viscosity of 1.8 dl./ g.and a gel content of less than 2%. Of the double bonds of this productdetectable by ultrared spectroscopy, 78% were present in thetrans-configuration.

Without ethanol in the catalyst system, the yield was only 9. 0 g.Without vinyl acetate, the yield was only 10.3 g. When both ethanol andvinyl acetate were omitted, the yield was only 1.7 g.

These experiments demonstrate that the activity of a catalyst consistingof tungsten hexachloride and ethylaluminum sesquichloride is increasedby more than a power of ten by the combined addition of ethanol andvinyl acetate.

EXAMPLE 19 AND COMPARATIVE EXPERIMENTS K, L, AND M Use ofdiethylaluminum chloride These experiments were conducted analogously toExample 18 and Comparative Experiments G, H, and J, except the samemolar amount of diethylaluminum chloride was employed in place ofethylaluminum sesquichloride.

With the simultaneous use of ethanol and vinyl acetate, 42.9 g. of apolypentenamer was obtained having a reduced specific viscosity of 2.2dl./g. and less than 2% of gel content. Of the detectable double bonds,78% were present in the trans-configuration- In the absence of ethanol,only 8.3 g. of a polymer was obtained. In the absence of vinyl acetate,the yield was only 11.8 g. In the absence of both of these additives,only 16.5 g. of polymer was produced.

The activating effect of the concomitant use of ethanol and vinylacetate is especially remarkable and surprising in this connection sinceeach additive by itself reduces the yield in polymer.

EXAMPLES 20-28 AND COMPARATIVE EXPERIMENTS N, 0, AND P Polymerization ofvarious cycloolefins Examples 20-28 and Comparative Experiments N-P wereconducted as described in Examples 1-16 and Comparative Experiments A-E.The solvent, in all cases, was technical hexane (boiling point limits6870 C.). The

15 16 amount of this solvent was selected so that the solutions, Fromthe foregoing description, one skilled in the art PYIOr t thepolymefllatlon, Contained 20% by Volume of can easily ascertain theessential characteristics of this ing g igg s g gg g g g 'i g g 352223333 2; Z vention, and without departing from the spirit and scopeworked up and then analyzed, in the manner already set thereof, can makevarious changes and modifications of the forth above. 5 invention toadapt it to various usages and conditions.

TABLE 2 Polymerization of various cycloolefins. Catalyst system: 0.5millimol of tungsten hexachloride/0.5 millimol of ethanol/varyingamounts of ethylaluminum dichloride. Polymerization temperature: 0.

Polymer EtAlClz Regulator Monomer in the Polymeri- Trans- Experlcatalystzation time (M01 Yield RSV content Gel ment No. Name (ML) (G.) (mmol)(hours) percent) Name (g.) (dl./g.) (percent) (percent) N 1 3 "V"'i""c"ti'gi 0.6 1.0 iny ace a e- 84 10.6 1.0 Methyl oleate 13.7 0.77 22 10.6 10 Octadecen-(9)yl acetate--- 21.6 0.90

172 8.2 .0 een- -y -aeeae 87 8.2 1.0 Allylchloroaeetate. 57.5 1.10 8.21.0 Vinyl stearate 45.3 1.66

4 57.4 2.3 l's'cyclooctadlene' 100 if'inyl isobutyrate I 12.1 1.0 Ethylundecenoate 28.5 0.56

N 0'1E.In Examples 20-25 and Comparative Experiments N and O, theRSV-values were measured in Decalln at 135 C.

COMPARATIVE EXPERIMENT SERIES Q-W What is claimed is:

1. A composition of matter suitable for the catalytic ring openingpolymerization of cyclic olefins, consisting essentially of:

Comparative Experiments Q-W were conducted in the manner described inExamples 116 and Comparative Experiments A-E. For each experiment, 100ml. (87.5 g.) of cyclododecene was employed as the monomer and 150 ml.of technical hexane (boiling point limits: 68-70 C.) was employed as thesolvent. The various conjugated dienes were utilized in varying amounts.The molar percent of diolefins set forth in Table 3 refers, in eachcase, to the cycloolefin employed. For each experiment, there wasemployed as the catalyst 0.5 millimol of tungsten hexa- 40 chloride, 0.5millimol of ethanol, and 3 millimols of ethylaluminum dichloride. In allexperiments the polymeriza- (a) A halide or oxyhalide of molybdenum ortungsten;

(b) An alkyl aluminum halide;

(c) A carboxylic acid ester containing at least one acycliccarbon-carbon double bond separated from the carbonyl ester grouping byat least one single bonded carbon atom or by the single bonded oxygenatom of the ester group, at least one of the double bonded carbon atomsof which bears a. hydrogen atom;

tion time was 2.5 hours at 20 C. The polymerizates were wherein themolar ratio of (a) to (b) is less than 1:1 and worked up in a mannerdescribed above and then analyzed. the ratio of (a) to (c) is less than100:1.

TABLE 3 Conjugated diolefin Polymer Experiment Mol Yield RSV TransSeries No. Name percent (g.) Percent (dl/g.) (percent) 21 23.3 (1.361,3-but d n 0 40 Q a 5 0.2 0.2 0.06 10 0. 3 0. 30 0. 07 46. 1 53. 0 2.25 46 1 47.1 54.2 1 07 44 R Isoprene 2 10. 1 11. 6 0. 94 52 5 No Polymers 2,3-dimethylbutadicue 3 3 33 52 i2 5 N o Polymer 37.8 43. 5 2 22 49 Tzkhexadiene 1 24.9 28.6 0 47 40 5 7.2 8.3 0 15 42 10 4 No Polymer UCyclopentadiene "i' 121% i312 5S 2% 10 12.2 14.0 34 45.3 5:3 2.16 431.02 V 1,3 cyclododecadlene 5 1' 8 2.1 10 1.5 1.7 3 egg 1. 63 41 W 1,3 lt d'ene 36 We a 1 5 8.1 9.3 1.52 40 10 4.0 4.6 1.10 43 1 Too littlesubstance. 1 Polymer contains insoluble components.

N o'rE.-All RSV-values were measured at 135 C. in Decalin.

The preceding examples can be repeated with similar 2. A compositionaccording to claim 1, wherein said success by substituting thegenencally or specifically dehalide or oxyhalide is a molybdenumcompound. scribed reactants and/or operating conditlons of this m- 3. Acomposition according to claim 1, wherein said vention for those used inthe preceding examples. halide or oxyhalide is a tungsten compound.

4. A composition according to claim 3, wherein said tungsten compound istungsten hexachloride or tungsten oxytetrachloride.

5. A composition according to claim 1, wherein said alkyl aluminumhalide is an alkyl aluminum chloride.

6. A composition according to claim 1, wherein said chloride is selectedfrom the group consisting of methyl aluminum dichloride, ethyl aluminumdichloride, methyl aluminum sesquichloride, ethyl aluminumsesquichloride, dimethyl aluminum chloride and diethyl aluminumchloride.

7. A composition according to claim 6, wherein said organoaluminumcompound is ethyl aluminum dichloride, ethyl aluminum sesquichloride, ordiethyl aluminum chloride.

8. A composition according to claim 7, wherein said organoaluminumcompound is ethyl aluminum sesquichloride or diethyl aluminum chloride.

9. A composition according to claim 8, wherein said halide or oxyhalideis a tungsten compound.

10. A composition according to claim 9, wherein said tungsten compoundis tungsten hexachloride or tungsten oxytetrachloride.

11. A composition according to claim 1, wherein the carboxylic acid of(c) is selected from the group consisting of alkanoic or cycloalkanoicsaturated monoand dicarboxylic acids containing 1-20 carbon atoms andsubstituted by -3 halogen atoms, and carbocyclic ary1mono anddicarboxylic acids containing 7-12 carbon atoms and substituted by 0-5halogen atoms.

12. A composition according to claim 11, wherein said ester is one ofthe formula wherein R and R each are hydrogen, alkyl, cycloalkyl, aryl,alkaryl or the corresponding halogenated groups, and a and d each are 0to 1, with the proviso that at least one a and d is l, and b and 0 eachare 0 or a positive integer.

13. A composition according to claim 12, wherein said carboxylic acidester is a vinyl or allyl ester.

14. A composition according to claim 11, wherein said carboxylic acidester is vinyl propionatc, vinyl isobutyrate, vinyl stearate, divinyladipate, methylvinyl adipate, vinyl pivalate, vinyl chloroacetate, allylpropionatc, allyl butyrate, allyl chloroacetate, allyl dichoroacetate ordiallyl phthalate.

15. A composition according to claim 14, wherein said carboxylic acidester is a vinyl ester.

16. A composition according to claim 15, wherein said carboxylic acidester is vinyl acetate.

17. A composition according to claim 13, wherein said carboxylic acidester is an allyl ester.

18. A composition according to claim 17, wherein said allyl ester isallyl acetate.

19. A composition according to claim 1, wherein the ratio of (a) :(c) isless than 10:1.

20. A composition according to claim 19, wherein said molar ratio isapproximately 0.02:1.

21. A composition according to claim 1, wherein the molar ratio of (b)(c) is greater than 1:1.

22. A composition according to claim 1, further comprising a catalystcomponent (d) containing one or more hydroxy or sulfhydryl groups andselected from the group consisting of water, hydrogen sulfide, hydrogenperoxide, and alkyl hydroperoxides.

23. A composition according to claim 1, further comprising a catalystcomponent (d) containing a saturated or unsaturated alcohol or phenolselected from the group consisting of n-propanol, n-butanol,sec-butanol, isobutanol, allyl alcohol, crotyl alcohol, phenol,o-cresol, mcresol, p-cresol, a-naphthol, fi-naphthol, eugenol and benzylalcohol.

24. A composition according to claim 23, wherein said component (d) isan alcohol.

25. A composition according to claim 24, wherein said alcohol isselected from the group consisting of methanol, ethanol, isopropanol andtert-butanol.

26. A composition according to claim 25, wherein said alcohol isethanol.

27. A composition according to claim 24, wherein said component (d) isphenol.

28. A composition according to claim 24, wherein the molar ratio of(a):(b) is about 1:0.1 to 1:2.

References Cited UNITED STATES PATENTS 3,259,610 7/1966 Grammer et al.252-429 B 3,449,310 6/1969 DallAsta et a1. 252-429 B 3,622,552 11/1971Fukuda et a1 252-429 B 3,631,010 12/1971 Witte et al. 252429 B PATRICKP. GARVIN, Primary Examiner US. Cl. X.R. 26093.l, 683.15 B

- UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent; N ,175Dated March 19, 1974 Inventor(s) Roland Streck, et al.

It is certified that error appears in the aboveidentified patent andthat said Letters Patent are hereby corrected as'shown below:

IN THE HEADING, COLUMN 1: Under "Claims priority,

application Germany, June 6, 1970, P 2028 935.4 should read Claimspriority, application Germany, Jane 12, 1970,

Signed and sealed this 3rd day' of December 1974.

' (SEAL) Attest:

McCOY M. GIBSON .JR. v c. MARSHALL DANN Arresting Officer I Commissionerof Patents UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION March19, 1974 Patent No. 3,798,175 Dated Inventor(s) Roland Streck, et a1.

It is certified that error appears in the above-identified patent andthat said Letters Patent are hereby corrected as shown below:

IN THE CLAIMS:

CLAIM 6, LINE 1 OF CLAIM, COLUMN 17: "claim 1" should be claim 5 (b)"should read CLAIM 28, LINE 2 OF CLAIM, COLUMN 18: "(a) Signed and sealedthis 16th day of July 1971 (SEAL) Attest:

MCCOY M. GIBSON, JR. C. MARSHALL DANN Attesting Officer Commissioner ofPatents USCOMM'DC 603764 69 fi U.SI GOVERNMENT PRINTING OFFICE: li!0-866-33L F ORM P O-105O (10-69)

